JP3430383B2 - Silver halide photographic emulsion and silver halide color photographic light-sensitive material - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic emulsion useful in the field of photography and a silver halide color photographic light-sensitive material using the same. More specifically, it relates to a silver halide photographic emulsion having improved sensitivity, graininess, fog and pressure resistance, and a silver halide color photographic light-sensitive material using the same.

[0002]

2. Description of the Related Art In recent years, performance requirements for silver halides for photography have become more and more severe, and for improvement of pressure resistance in silver halide color photographic light-sensitive materials against photographic characteristics such as high sensitivity and excellent graininess. Requests are also increasing more than ever before.

Various pressures are generally applied to a photographic light-sensitive material coated with a silver halide emulsion. For example, a negative film for general photography is bent or rubbed when it is wound in a cartridge or loaded in a camera, and is also subjected to great pressure during cutting and processing.

As described above, it is generally known that photographic performance changes when various pressures are applied to the photographic light-sensitive material, and a photographic light-sensitive material that does not change in photographic performance with respect to these pressures is generally known. It is strongly desired to provide.

As a means for improving the pressure characteristics, a method of incorporating a plasticizer such as a polymer or an emulsion or a method of reducing the silver halide / gelatin ratio of a silver halide emulsion is used to reach the pressure. It is known to prevent it. However, at present, it is difficult to achieve a sufficient effect by any of the methods.

In response to the demand for improved pressure characteristics, emulsions composed of core / shell type silver halide grains having a silver iodobromide layer having a high silver iodide content have been actively studied. As an example of high sensitivity and improvement of pressure resistance, an emulsion having a high silver iodide content inside the grain is disclosed in JP-A-59-99433.
JP-A-60-35726, JP-A-60-1477
No. 26 is disclosed in each publication. However, when these examples were additionally tested, the effect of improving pressure resistance was insufficient. Further, in Japanese Patent Laid-Open No. 3-189642,
Graininess is improved and fog is reduced by introducing a dislocation line into the fringe portion of the grain, but the pressure resistance is significantly deteriorated, and the sensitivity is reduced due to the application of pressure after exposure.

Further, in Japanese Patent Laid-Open No. 4-251241, dislocation lines are introduced into the principal plane region of grains to improve fog and pressure fog, but these performances are still satisfactory. However, deterioration of the graininess was observed.

Further, in JP-A-6-332093, an emulsion having an aspect ratio of 8 or more and containing a dislocation line is used to improve sensitivity and to improve pressure resistance, but the improvement effect is insufficient and the graininess is poor. Accompanied by deterioration. Structurally this application
With respect to the invention of claim 1, mainly {111} and {10}
Tabular silver halide grains consisting of
The point is that there are 10 or more dislocation lines per grain in the plane region.
In addition, the higher the aspect ratio, the more unstable the edge part of the particle becomes, and the shape of the hexagonal flat plate is such that the circular flat plate in which the edge part is melted becomes mixed.
Performance between particles did not reach a level that could be practically used.

Furthermore, European patent EP 0515894A1
In No. 6, an emulsion having a {100} plane at the edge of a flat plate with a high aspect ratio of {111} plane as the main plane and being doped with a Group 8 metal cyano complex realizes high sensitivity and low fog. However, the graininess was rather deteriorated.

[0010]

In contrast to the above problems, the object of the present invention is to improve the above problems by improving the sensitivity and graininess, and improving fog and pressure fog. It is intended to provide a silver halide photographic emulsion and a silver halide color photographic light-sensitive material.

[0011]

As a result of earnest research, the present inventors have found that the object of the present invention can be achieved by the following.

(1) In a silver halide photographic emulsion containing silver halide grains in a dispersion medium, the grain size distribution of the silver halide grains is monodisperse, and the total projected area of the silver halide grains is 50. % Has an aspect ratio of 8 or more and is mainly composed of {111} and {100} planes 6
Is the angular tabular silver halide grains, the {100} plane is the
A silver halide photographic emulsion which appears at the edge of a tabular silver halide grain and has 10 or more dislocation lines per grain in the main plane area of the grain.

[0013] (2) tabular silver halide photographic emulsion according to Item 1, wherein no dislocation lines in the edge portion of the main planes of the silver halide grains.

(3) In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is a silver halide photographic emulsion as described in the above item 1. A silver halide color photographic light-sensitive material characterized by containing.

(4) In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is the silver halide photographic emulsion as described in the above item 2. A silver halide color photographic light-sensitive material characterized by containing.

Hereinafter, each invention of the present application will be described in detail.

The silver halide photographic emulsion of the present invention contains, as silver halide, silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, silver chloroiodide and silver chloride. Although any of those used for the usual silver halide emulsions can be used, silver bromide, silver iodobromide and silver chloroiodobromide are particularly preferable.

The silver halide grain according to the present invention may be either a grain in which a latent image is mainly formed on the surface or a grain in which the latent image is mainly formed inside the grain.

In the silver halide grains according to the present invention, 50% or more of the total projected area has an aspect ratio (grain size / grain thickness ratio) of 8 or more, more preferably 12 or more, still more preferably 15 or more. is there.

The grain size (ri) is the diameter of a circle having an area equal to the projected area of the grain when the silver halide grain is observed with a microscope or an electron microscope, and the grain thickness is parallel to each other. The distance between the outer surfaces. The particle thickness can be calculated by depositing a metal from the oblique direction of the particle together with the latex for reference, measuring the shadow length of the metal on an electron microscope, and referring to the shadow length of the latex.

In the present invention, the average aspect ratio is the average of the aspect ratios of all tabular grains in the emulsion, and the tabular grains are grains having an aspect ratio of 2 or more.

The tabular silver halide grains of the present invention occupy 50% or more of the projected area of all silver halide grains, but preferably 60% or more.

The silver halide grains of the present invention are monodisperse emulsions.

The monodisperse emulsion of the present invention is 20% or less when the width of distribution is defined by (standard deviation / average grain size) × 100 = width of distribution (variation coefficient) [%]. It is more preferably 15% or less.

The average particle size and standard deviation are obtained from the particle size ri defined above.

In the present invention, the silver halide grains preferably have two twin planes parallel to each other, and are tabular silver halide grains having two twin planes parallel to the principal plane. It is preferable.

The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First,
A sample is prepared by coating a silver halide photographic emulsion on a support so that the tabular silver halide grains contained therein are oriented substantially parallel to each other. This is cut with a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. The presence of twin planes can be confirmed by observing this section with a transmission electron microscope.

The silver halide grains contained in the silver halide emulsion of the present invention are hexagonal flat plates in shape.

The silver halide grains contained in the silver halide emulsion of the present invention are mainly composed of {111} faces and {100} faces.

In the present invention, the {111} plane and the {1} are mainly used.
Consisting of {00} faces means that the surface of the silver halide grain is {1
11} planes and {100} planes are present, and the ratio of {111} planes to the total surface of the silver halide grain is {1}.
It means that the sum of the proportion of the {00} planes is 60% or more.

In the present invention, it is preferable that 50% or more of the total projected area of the silver halide grains have {111} faces and {100} faces on the surface of one silver halide grain.
It is more preferably 60% or more, and most preferably 70% or more.

In the present invention, the ratio of {100} planes of tabular grains is such that the {111} planes and {10} planes in the adsorption of sensitizing dyes are {10}.
0} plane and a method that utilizes the difference in adsorption dependence, for example, T.
It can be determined by the method described in Tani, J. Imaging Sci., 29, 165 (1985) and the like.

In this study, the area ratio (Cub) of the {100} plane can be obtained by the following equation.

Cub = [W (d) × NA × S (d)] / [M
w (d) × S (g)] × 100 [%] where, W (d): Saturated adsorption amount of the dye on the non- {111} plane NA: Avogadro's number S (d): 1 dye molecule occupies Area Mw (d): Molecular weight S (g) of dye: Total particle surface area.

Further, the area ratio (ECub) of the {100} plane of the edge portion can be obtained by the following equation.

[0036] ECub = Cub × (ECD + 2t) / 2t here, ECD: Particle size t: particle thickness Represents

The area ratio of the {100} plane in the edge portion is preferably 15% or more, more preferably 30% or more, further preferably 50% or more.

In the present invention, the appearance location of the {100} plane is the edge portion of the hexagonal flat plate.

In the silver halide emulsion of the present invention, {1
To control the {00} plane ratio, see Japanese Patent Application Laid-Open No. 2-29.
The description such as 8935 can be referred to. More specifically, controls such as silver halide grain growth pAg, silver halide solvent concentration, and silver halide grain growth pH are preferably used. It can also be controlled by the presence of a compound represented by the following general formula [I].

More preferably, the presence of these compounds is controlled or the growth pAg is controlled.

General formula [I] YO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _p (C
H ₂ CH ₂ O) in _n Y formulas, Y is a hydrogen atom, -SO ₃ M or -COBCOO
Represents M. M represents a hydrogen atom, an alkali metal atom, an ammonium group or an alkyl-substituted ammonium group having 5 or less carbon atoms, and B represents a chain or cyclic group forming an organic dibasic acid. m and n each represent 0 to 50, and p represents 1 to 100.

Typical examples of the compounds represented by the general formula [I] are shown below.

[0043]

[Chemical 1]

In the present invention, the addition amount of these compounds is preferably 5 × 10 ^-2 g to 10 g per mol of silver.

In the present invention, the silver iodide content and the average silver iodide content of each silver halide grain are determined by the EPMA method (El
ectron Probe Micro Analyzer method). According to this method, a sample in which emulsion grains are well dispersed so as not to come into contact with each other is prepared, and elemental analysis of an extremely minute portion can be performed as compared with X-ray analysis by electron beam excitation of electron beam irradiation.

By this method, the halogen composition of each grain can be determined by obtaining the characteristic X-ray intensity of silver and iodide emitted from each grain. If the silver iodide content of at least 50 grains is determined by the EPMA method,
The average silver iodide content is determined from the average of them.

In X-ray photoelectron spectroscopy, the emulsion is pretreated as follows prior to its measurement. First, the emulsion is about 1m
10 ml of 0.01 wt% aqueous solution of pronase was added to
Gelatin is decomposed by stirring at 40 ° C. for 1 hour. Next, the emulsion particles are settled by centrifugation, the supernatant is removed, 10 ml of a pronase aqueous solution is added, and gelatin is decomposed again under the above conditions. Centrifuge the sample again,
After removing the supernatant, 10 ml of distilled water is added to redisperse the emulsion particles in distilled water, and the mixture is centrifuged to remove the supernatant. After repeating this washing operation three times, the emulsion grains are redispersed in ethanol (the work up to this point is performed in a dark room). This is thinly coated on a mirror-polished silicon wafer in a dimly lit room to obtain a measurement sample. The sample coated on the silicon wafer is measured by X-ray photoelectron spectroscopy within 24 hours.

For measurement by X-ray photoelectron spectroscopy, an ESCA / SAM560 type manufactured by PHI is used as an apparatus.
The sample is fixed to a 60-degree tilt holder, and the sample pre-evacuation chamber is evacuated for 10 minutes using a turbo molecular pump, and then introduced into the measurement chamber. Irradiation of excitation X-rays (Mg-Kα rays) is started within 1 minute after introduction of the sample, and measurement is started immediately.

The measurement is performed under the conditions of an X-ray source voltage of 15 kV and an X-ray source current of 40 mA and a pass energy of 50 eV.

Ag3 was used to determine the surface halide composition.
Detects d, Br3d, and I3d3 / 2 electrons. Ag3d
For detecting electrons, the binding energy is from 381eV to 361eV.
V range scan 0.2 eV, each step 1
The measurement is performed once every 00 msec, the total energy is 79 eV to 59 eV for detection of Br3d electrons, and the scan step is 0.2 eV, each measurement is performed for 100 msec five times, and the total energy is from 644 eV to 624 eV for detection of I3d3 / 2 electrons. The range is measured 40 times with a scan step of 0.2 eV and each step of 100 msec. The data is obtained by repeating the above operation twice.

The integrated intensity of each peak is used to calculate the composition ratio. The integrated intensity of the Ag3d peak is a straight line connecting the intensity of the energy value obtained by adding 4eV to the total energy at which the Ag3d5 / 2 peak shows the maximum value and the intensity of the energy value obtained by adding 4eV to the binding energy at which the Ag3d5 / 2 peak shows the maximum value. The baseline is calculated in units of cps · eV, and the integrated intensity of the Br3d peak is calculated from the intensity of the energy value obtained by adding 4eV to the total energy at which the Br3d5 / 2 peak has the maximum value and the total energy at which the Br3d5 / 2 peak has the maximum value. The straight line connecting the intensities of the energy values reduced by 3 eV is used as the baseline, and the integrated intensity of the I3d3 / 2 peak is the intensity of the energy value obtained by adding 4 eV to the total energy at which the I3d3 / 2 peak has the maximum value. , I3d3 / 2 peak shows the maximum value. 4eV from total energy Flip was seeking straight line connecting the intensity of the energy values in units of cps · eV and baseline.

When the composition ratio is calculated from the integrated intensity of each peak, the relative sensitivity coefficient method is used and Ag3d and Br3 are used.
5.1 as the relative coefficient of d and I3d3 / 2, respectively.
By using 0, 0.81, and 4.592, the composition ratio is given in atomic percent. I mole percent is determined by dividing the atomic percent value of I by the atomic percent value of Br and the atomic percent value of I.

The emulsion of the present invention preferably has a more uniform iodine content between grains.

The silver halide grains according to the present invention preferably have a more uniform iodide content between grains.
When the distribution of the iodide content between grains is measured by the EPMA method, the relative standard deviation is preferably 35% or less, more preferably 20% or less.

The average silver iodide content of the emulsion of the present invention is preferably 2 to 12 mol%.

The dislocations of the silver halide grains according to the present invention are described, for example, in JF Hamilton, Phot.Sci.Eng., Vol11,57.
(1967), T. Shiozawa, J.Soc.Phot.Sci.Japan, vol35,21
3 (1972) and can be observed by a direct method using a transmission electron microscope at low temperature. That is,
Place the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion, place on a mesh for electron microscope observation, and cool the sample to prevent damage (printout etc.) due to electron beams. Observe by the transmission method in the state. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to more clearly observe using a high-voltage electron microscope (200 kV or more for particles having a thickness of 0.25 μm). .

From the photograph of the grains obtained by such a method, the position and number of dislocations of each grain when viewed from the direction perpendicular to the principal plane can be determined.

In the emulsion of the present invention, the proportion occupied by tabular silver halide grains having 10 or more dislocation lines per grain in the main plane region of the tabular grains is preferably 30% or more.

The principal plane region of the tabular grains means a region having a certain thickness including outer surfaces composed of facing parallel planes.

The opposing parallel planes are preferably {111} planes.

Further, according to the present invention, it is possible to allow dislocations to exist in the main plane region excluding the edge portion of the main plane. The term "edge portion" as used herein refers to a circle having an area equal to that of the main plane, and exists around a tabular grain having an area corresponding to an annular region that is 5% in the radial direction from the circumference of the circle. The area having the thickness of tabular grains. The central region of the tabular grains referred to herein has a radius of 10% of the radius of a circle having the same area as the principal plane of the grain and is the thickness of the tabular grains in a circular portion having a common center. It is the area that it has. The dislocation of the present invention is not localized at a specific position in a region including the main plane of the host grain like the edge portion and the central region.

The feature of tabular grains is that the area of the principal plane is large relative to the grain volume, and the introduction of dislocations into the large principal plane region maximizes the merit of tabular grains. Become. In the present invention, the ratio of the area of the main plane having 10 or more dislocations per grain to the total main plane area is at least 10% to 100%, preferably 30% to 100%.

The tabular grains according to the present invention generate a large number of minute silver chloride or silver chlorobromide epitaxies on the principal plane with respect to the base tabular grains, and then the physical ripening of the epitaxy and And / or halogen conversion, and further shell growth to obtain dislocations.

The amount of silver salt (mainly silver nitrate) and halide necessary for depositing epitaxy on the tabular grains according to the present invention is 0.1 to 30 mol%, preferably 0.5 to 20 mol% of the host grains. , And more preferably 1 to 10
It is mol%.

The amount of halogen required to convert the epitaxy deposited on the tabular grains according to the present invention is preferably 5 to 100 mol%, more preferably 10 to 5 based on the amount of silver epitaxially grown.
It is 0 mol%. The halogen used is iodide, a combination of iodide and bromide, or bromide, and is added as an aqueous solution. As a method of adding these, it is preferable to add them as fine particles. These fine particles are usually 0.01
The particle size is not less than μm and not more than 0.1 μm, but 0.0
Fine particles having a particle size of 1 μm or less or 0.1 μm or more can also be used.

The amount of the tabular grain shell according to the present invention is
The amount of silver may be 5 mol% or more with respect to the host particles. The halogen composition of the shell is arbitrary and may be any of silver chloride, silver bromide, silver iodobromide, silver chloroiodobromide and silver chlorobromide.

The silver halide grains according to the present invention may be those obtained by any of the acidic method, the neutral method and the ammonia method, and the method of reacting a soluble silver salt with a soluble silver halide is a side mixture. Any of a method, a simultaneous mixing method, and a combination thereof may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the simultaneous mixing method, a method of keeping pAg constant in a liquid layer in which silver halide is produced, that is, a so-called controlled double jet method can be used.

Further, two or more kinds of silver halides formed separately may be mixed and used.

The silver halide grains according to the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), indium salt and rhodium during the grain forming process and / or the growing process. A metal ion can be added using at least one selected from a salt (including a complex salt) and an iron salt (including a complex salt), and these metal elements can be contained inside and / or on the surface of the particle.
Further, by placing in an appropriate reducing atmosphere, reduction sensitizing nuclei can be imparted to the inside and / or the surface of the grain.

As a method for obtaining a monodisperse emulsion, two or more kinds of reactions arbitrarily selected from a water-soluble silver salt solution, a water-soluble halide solution, and silver halide fine particles in a gelatin solution containing seed particles. Elements can be obtained by adding under controlled pAg and pH. In determining the addition rate, JP-A-54-48521 and JP-A-5-51821 are used.
Reference can be made to No. 8-49938.

As a method for obtaining a more advanced monodisperse emulsion, the growth method in the presence of tetrazaindene disclosed in JP-A-60-122935 can be applied.

A known silver halide solvent such as ammonia, thioether or thiourea may be present during the production of the silver halide grains according to the present invention, or the silver halide solvent may not be used.

The silver halide grains according to the present invention are produced in the presence of a dispersion medium, that is, in a solution containing the dispersion medium.

Here, the aqueous solution containing a dispersion medium refers to an aqueous solution in which a protective colloid is formed by a substance such as gelatin or a substance capable of forming a binder such as a substance capable of forming a hydrophilic colloid, and preferably a colloidal form. An aqueous solution containing the protected gelatin of

When gelatin is used as the protective colloid in carrying out the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in Arthur Guice, The Macromolecular Chemistry of Gelatin, (Academic Press, 1964).

Hydrophilic colloids other than gelatin that can be used as protective colloids include, for example, gelatin derivatives, graft polymers of gelatin and other polymers,
Proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
There are various types of synthetic hydrophilic polymeric substances such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers.

In the case of gelatin, it is preferable to use one having a jelly strength of 200 or more in the Paggy method.

The silver halide grains according to the present invention may be those in which unnecessary soluble salts have been removed after the growth of the silver halide grains has been completed, or they may be contained as they are.

Further, as in the method described in JP-A-60-138538, desalting can be carried out at any point in silver halide growth. The removal of the salts can be carried out according to the method described in Research Disclosure (hereinafter abbreviated as RD) 17643, Item II. More specifically, in order to remove the soluble salt from the emulsion after the precipitation or after the physical ripening, a Nudel water washing method performed by gelatinizing gelatin may be used, and inorganic salts, anionic surfactants, A precipitation method (flocculation) using an anionic polymer (for example, polystyrenesulfonic acid) or a gelatin derivative (for example, acylated gelatin, carbamoylated gelatin, etc.) may be used.

The silver halide grains according to the present invention can be chemically sensitized by a conventional method. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using a gold or other noble metal compound can be used alone or in combination.

The silver halide grain according to the present invention can be optically sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more kinds. A dye that does not have a spectral sensitizing effect by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing effect of the sensitizing dye is included in the emulsion. May be.

Antifoggants, stabilizers and the like can be added to the silver halide grains according to the present invention. It is advantageous to use gelatin as the binder. The emulsion layer and other hydrophilic colloid layers may be hardened and may contain a plasticizer and a dispersion (latex) of a water-insoluble or soluble synthetic polymer.

A coupler is used in the emulsion layer of the color light-sensitive material. Further, by a coupling with a competing coupler having an effect of color correction and an oxidized product of a developing agent, a development accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a fogging agent, an antifoggant, Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers and desensitizers can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an anti-irradiation layer. In these layers and / or in the emulsion layers, dyes which may be bleached or bleached from the light-sensitive material during development processing may be contained.

Matting agents, lubricants, image stabilizers, formalin scavengers, ultraviolet absorbers, fluorescent whitening agents, surfactants, development accelerators and development retarders can be added to the light-sensitive material.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

[0088]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited thereto.

Example 1 [Preparation of Twin Crystal Emulsion T-1] By the method described below,
A seed emulsion having two parallel twin planes was prepared.

A: Oscein gelatin 80.0 g potassium bromide 47.4 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) in a 10% by weight methanol solution 0.48 ml finished with distilled water to 8000.0 ml B: silver nitrate 1200.0 g finished with distilled water to 1600.0 ml C: ossein gelatin 32.2 g potassium bromide 823 0.8 g Potassium iodide 23.45 g Distilled water finishes to 1600.0 ml D: Ammonia water 470.0 ml Liquid A stirred vigorously at 40 ° C. and liquid B and liquid C for 7.7 minutes by the double jet method. Was added to generate nuclei. During this period, pBr was kept at 1.60.

Thereafter, the temperature was lowered to 20 ° C. over 30 minutes. Furthermore, the D liquid was added in 1 minute, and the aging was continued for 5 minutes. KBr concentration during aging is 0.03m
The ol / l and the ammonia concentration were 0.66 mol / l.

After completion of the aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. 10% by weight in the emulsion after desalting
The gelatin aqueous solution was added, and the mixture was stirred and dispersed at 60 ° C. for 30 minutes, and distilled water was added to complete an emulsion of 5360 g.

When the seed emulsion grains were observed with an electron microscope, they were tabular grains having two parallel twin planes.

The average grain size of the seed emulsion grains is 0.295 μm.
The number of particles having m, an average aspect ratio of 5.0, and two parallel twin planes was 80% (the number ratio) of all particles.

[Preparation of Comparative Emulsion EM-1] 7 shown below
Comparative emulsion EM-1 was prepared using different types of solutions.

(Solution A) Ocein gelatin 67.0 g Distilled water 3176.0 ml HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by weight methanol solution 2.50 ml Seed emulsion (T-1) 98.51 g Distilled water finishes to 3500 ml (solution B) 3.5N silver nitrate aqueous solution 4606 ml (solution C) potassium bromide 1915. 1 g ossein gelatin 200 g Finish to 4606 ml with distilled water (solution D) Fine grain emulsion (*) 2465.5 g * Preparation method consisting of 3% by weight of gelatin and silver iodide grains (average grain size 0.05 μm) Is shown below.

6.0 containing 0.06 mol of potassium iodide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added to 5000 ml of a weight% gelatin solution over 10 minutes.

The pH during fine particle formation was 2.0 using nitric acid.
The temperature was controlled at 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. The finished weight was 12.53 kg.

(Solution E) 1.75N aqueous solution of potassium bromide A solution A was added to a reaction vessel, and while vigorous stirring, solutions B to D were added by the simultaneous mixing method to grow seed crystals, A shell type silver halide emulsion was prepared. Up to 65% of the total amount of silver added, solution C and D were added in a molar ratio of 9: 1, and after 65%, only solution B and solution C were added.

Here, (1) Solution B, Solution C and Solution D
The addition rate of (2) solution B and solution C is
Each of them is changed in a function-like manner with respect to time so as to correspond to the critical growth rate of silver halide grains, and an appropriate addition rate is added so as not to cause polydispersion due to generation of small grains other than growing seed crystals and Ostwald ripening. Controlled.

Further, the temperature of the solution in the reaction vessel was controlled at 75 ° C. and the pAg was controlled at 9.0 over the entire area of the crystal growth. Solution E was added as needed for pAg control.

Thereafter, desalting treatment was performed according to the method described in JP-A-5-72658, gelatin was added, and the temperature was 50 ° C.
Re-disperse for 30 minutes, cool to 40 ° C and adjust pH to 5.8.
0, pAg was adjusted to 8.06. From an electron micrograph of the obtained emulsion grains, it was confirmed that the grains were tabular grains having an average grain size of 1.99 μm, an average aspect ratio of 8.5 and a grain size distribution of 18.0%. [Preparation of Comparative Emulsion EM-2] In the production method of Emulsion EM-1, Solution B to
The addition of solution D was stopped, and solution D corresponding to 2 mol% of the total amount of silver added was added in 2 minutes, followed by ripening for 10 minutes,
After further addition, pAg was lowered to 8.0 at the time when 85% of the total amount of added silver was completed, and otherwise the emulsion EM-1.
Emulsion EM-2 of the present invention was prepared by the same production method as described above.

[Preparation of Emulsion EM-3 of the Present Invention] Emulsion EM-
In the production method of 2, the addition of solutions B to D was stopped at the time when 65% of the total added silver amount was completed, the temperature was lowered to 40 ° C., pAg was adjusted to 6.6, and 10 mol of the total added silver amount was adjusted. %
A 0.35M silver nitrate solution corresponding to the above was added simultaneously with the same amount of 0.8M NaCl over 10 minutes. The temperature was again raised to 75 ° C., aging was carried out for 10 minutes, and pAg was adjusted to 8.
After being adjusted to 0, addition was continued by the same production method as for the emulsion EM-1 to prepare the emulsion EM-3 of the present invention.

[Preparation of Emulsions EM-4 and EM-5 for the Present Invention] In the method for producing the emulsion EM-3, the total addition amount of silver was 6
Emulsions EM-4 and EM-5 of the present invention were prepared by the same production method as Emulsion EM-3, except that the pAg until the completion of 5% was raised above 9.0.

[Preparation of Comparative Emulsion EM-6] Emulsion EM-
Comparative Emulsion EM-6 was prepared in the same manner as in Emulsion EM-3, except that pAg until 65% of the total amount of added silver was changed to 8.4.

[Preparation of Comparative Emulsion EM-7] Emulsion EM-
Comparative Emulsion EM-7 was prepared in the same manner as in Emulsion EM-3 except that pAg was adjusted to 8.4 until 65% of the total amount of added silver was completed.

Table 1 shows the characteristics of emulsions EM-1 to EM-7.

[0108]

[Table 1]

As can be seen from Table 1, in the emulsion grown by epitaxy during the growth of silver halide grains, generation of dislocation lines is recognized in the main plane region of the grain. Also, {1
The {00} plane ratio usually decreases as the aspect ratio increases, but by lowering the pAg of the shell, the {100} plane appears at the edge portion and the {100} plane ratio also rises. I understand.

Example 2 (Preparation of Photosensitive Material Sample) EM-1 to EM-7 were subjected to gold-sulfur sensitization, and these emulsions were used to prepare a composition as shown below on a triacetyl cellulose film support. Each layer was sequentially formed from the support side to prepare a multicolor photographic light-sensitive material.

In all the following descriptions, the addition amount in the silver halide photographic light-sensitive material is 1 m unless otherwise specified.
^The number of grams per ² is shown. Further, silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes are shown in the number of moles per mole of silver halide.

The constitution of the multiple color photographic light-sensitive material sample-1 (using the comparative emulsion EM-1) is as follows.

Sample 1 First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: low sensitivity red sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0. 35 Sensitizing dye (SD-1) 2.0 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.4 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.4 × 10 ⁻⁵ Sensitizing dye ( SD-4) 0.7 × 10 ^-4 Cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) 0.04 DIR compound (D-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 Fourth layer: Medium-sensitive red-sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide Increase agent C 0.34 Sensitizing dye (SD-1) 1.7 × 10 -4 Sensitizing dye (SD-2) 0.86 × 10 -4 Sensitizing dye (SD-3) 1.15 × 10 -5 Sensitizing dye (SD-4) 0.86 × 10 ⁻⁴ Cyan coupler (C-1) 0.33 Colored cyan coupler (CC-1) 0.013 DIR compound (D-1) 0.02 High boiling point solvent ( OIL-1) 0.16 Gelatin 0.79 Fifth layer: High-sensitivity red-sensitive layer Silver iodobromide emulsion D 0.95 Sensitizing dye (SD-1) 1.0 × 10 ⁻⁴ Sensitizing dye (SD- 2) 1.0 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.2 × 10 ⁻⁵ Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point solvent (OIL) -1) 0.16 Gelatin 0.79 Sixth layer: intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.1 1 gelatin 0.80 7th layer: low-sensitivity green sensitive layer silver iodobromide emulsion A 0.12 silver iodobromide emulsion B 0.38 sensitizing dye (SD-4) 4.6 × 10 ^-5 sensitizing dye (SD-5) 4.1 × 10 ⁻⁴ Magenta coupler (M-1) 0.14 Magenta coupler (M-2) 0.14 Colored magenta coupler (CM-1) 0.06 High boiling point solvent (OIL-4) ) 0.34 gelatin 0.70 Eighth layer: intermediate layer Gelatin 0.41 Ninth layer: medium-sensitive green sensitive layer Emulsion EM-1 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-6) ) 1.2 × 10 ^-4 sensitizing dye (SD-7) 1.2 × 10 ^-4 sensitizing dye (SD-8) 1.2 × 10 ^-4 magenta coupler (M-1) 0.04 magenta coupler (M-2) 0.04 Colored magenta coupler (CM-1) 0.017 DIR compound (D-2) .025 DIR compound (D-3) 0.002 high boiling point solvent (OIL-4) 0.12 gelatin 0.50 10th layer: high sensitivity green sensitive layer silver iodobromide emulsion D 0.95 sensitizing dye (SD -6) 7.1 x 10 ^-5 sensitizing dye (SD-7) 7.1 x 10 ^-5 sensitizing dye (SD-8) 7.1 x 10 ^-5 magenta coupler (M-1) 0.09 Colored magenta coupler (CM-1) 0.011 High boiling point solvent (OIL-4) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point Solvent (OIL-2) 0.19 Gelatin 1.10 Layer 12: Low sensitivity blue sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 increase Sensitizing dye (SD-9) 6.3 × 10 ⁻⁵ Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 High boiling point solvent (OIL- 2) 0.42 Gelatin 1.40 13th layer: High-sensitivity blue-sensitive layer Silver iodobromide emulsion C 0.15 Silver iodobromide emulsion E 0.80 Sensitizing dye (SD-9) 8.0 × 10 ^{− 5} Sensitizing dye (SD-11) 3.1 × 10 ⁻⁵ Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Iodine Silver bromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 High boiling point solvent (OIL-1) 0.07 High boiling point Solvent (OIL-3) 0.07 Gelatin 0.65 Fifteenth layer: Second protective layer Alkali-soluble ma Agent (average particle size 2 μm) 0.15 polymethylmethacrylate (average particle size 3 μm) 0.04 slip agent (WAX-1) 0.04 gelatin 0.55 In addition to the above composition, a coating aid Su- 1. Dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, average molecular weight: 10,000
0 and average molecular weight: 1,100,000 two AF-
2, and preservative DI-1 was added.

The emulsions used for the above samples are as follows. The average particle size is shown as a particle size converted into a cube.
Further, each emulsion was optimally subjected to gold / sulfur sensitization.

[0115]

[Table 2]

[0116]

[Chemical 2]

[0117]

[Chemical 3]

[0118]

[Chemical 4]

[0119]

[Chemical 5]

[0120]

[Chemical 6]

[0121]

[Chemical 7]

[0122]

[Chemical 8]

[0123]

[Chemical 9]

[0124]

[Chemical 10]

[0125]

[Chemical 11]

[0126]

[Chemical 12]

The emulsions EM-2 to EM-7 are also shown in Table 3.
As shown in (1), by using each of these emulsions in place of the emulsion EM-1 of Sample-1, multiple color photographic light-sensitive material samples-2 to 7 were similarly prepared.

[0128]

[Table 3]

After subjecting each of the samples prepared as described above to wedge exposure using green light (G),
The following development processing was performed and the relative sensitivity, graininess, and pressure resistance were measured.

Treatment process time Temperature 1. Color development 3 minutes 15 seconds 38.0 ± 0.1 ° C 2. Bleach 6 minutes 30 seconds 38.0 ± 3.0 ° C 3. Washing with water 3 minutes 15 seconds 24-41 ° C 4. Stationary 6 minutes 30 seconds 38.0 ± 3.0 ° C 5. Washing with water 3 minutes 15 seconds 24-41 ° C 6. Stability 3 minutes 15 seconds 38.0 ± 3.0 ° C 7. Dryness 50 ° C or less The composition of the treatment liquid used in each treatment step is as follows.

[0131] <Color developer> 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) Aniline / sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid / trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter and adjust to pH = 10.1.

[0132] <Bleaching solution> Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water is added to make 1 liter, and the pH is adjusted to 6.0 using aqueous ammonia.

[0133] <Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 1 liter and adjust to pH = 6.0 with acetic acid.

[0134] <Stabilizer> Formalin (37% aqueous solution) 1.5 cc Conidax (manufactured by Konica Corporation) 7.5 cc Add water to make 1 liter.

The results obtained are shown in Table 4.

[0136]

[Table 4]

The relative sensitivity is Dmin (minimum density) +0.
It is the relative value of the reciprocal of the exposure dose that gives a density of 1.
The sensitivity immediately after preparation of the sample No. 1 was shown as 100 (1
The larger the value is, the higher the sensitivity is.

Fog is Dmin (minimum density),
The value immediately after the preparation of the sample of Sample-1 was shown as 100 (the larger the value with respect to 100, the higher the fog).

Regarding pressure fog, 23 ° C., 55%
Under the conditions of (relative humidity), using a scratch strength tester (manufactured by Shinto Kagaku Co., Ltd.), a needle with a radius of curvature of 0.025 mm is 5
After applying a load of g and scanning at a constant speed, exposure and development are performed, and the density change (ΔDp) of the portion under load at a density of Dmin is obtained, and ΔDp1 of Sample-1 is set to 1
The value is set to 00 (the smaller the value relative to 100, the better the improvement).

The RMS value was obtained by scanning the concentration of the measured portion of the sample with a microdensitometer having an aperture scanning area of 1800 μm ² (slit width 10 μm, slit length 180 μm), and measuring the concentration value variation of 1000 or more concentration measurement samplings. The value is shown as a relative value with 1000 times the standard deviation as 100.

As is clear from the results shown in Table 4, samples of the present invention containing the emulsions EM-3, 4, 5 according to the present invention-
Nos. 3, 4, and 5 have high sensitivity, improved graininess, low fog, and reduced pressure fog. Among these, Emulsion EM-5 satisfying the best combination of the present invention.
Sample-5 using is particularly excellent.

As described above, according to the invention of the present application, a silver halide photographic light-sensitive material excellent in sensitivity, graininess, fog and pressure fog can be obtained.

[0143]

Industrial Applicability A silver halide photographic emulsion and a silver halide color photographic light-sensitive material having excellent sensitivity, graininess, fog and pressure fog resistance can be obtained.

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 1/035 G03C 7/00 510 G03C 7/00 520

Claims (4)

(57) [Claims] 1. In a silver halide photographic emulsion containing silver halide grains in a dispersion medium, the grain size distribution of the silver halide grains is monodisperse, and 50% of the total projected area of the silver halide grains is 50%. The above is a hexagonal tabular silver halide grain having an aspect ratio of 8 or more and mainly composed of {111} and {100} planes, the {100} plane being the flat plane.
A silver halide photographic emulsion which appears at the edge portion of a tabular silver halide grain and has 10 or more dislocation lines per grain in the main plane area of the grain. 2. A flat according to claim 1, wherein silver halide photographic emulsion having no dislocation lines in edge portions of the main planes of the silver halide grains. 3. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers contains the silver halide photographic emulsion according to claim 1. A silver halide color photographic light-sensitive material characterized in that 4. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers contains the silver halide photographic emulsion according to claim 2. A silver halide color photographic light-sensitive material characterized in that